Cellulose derivatives



Patented Mar. 9, 1937 PATENT OFFICE UELLULQSE DERIVATIVES Henry Dreyfus, London, England No Drawing. Application December 15, 1932,

Serial No. 647,433. In Great Britain January Claims.

This invention relates to the manufacture and application of new nitrogen-containing cellulose derivatives.

In my U. S. Patent No. 2,007,950,- I have de- 5 scribed inter alia the manufacture of new cellulose derivatives by treating carboxy or hydroxy esters or ethers of cellulose so as to replace the simple hydroxy groups or hydroxy radicles in the carboxy groups by substituted amino groups.

0 Such substitution may take place either directly or by first halogenating the ester or ether and replacing the halogen'atomor atoms with the substituted amino groups. I have now found that further new nitrogen-containing cellulose derivatives may be obtained by treatment with nitrogen-containing organic compounds of celluloseesters or ethers containing unsaturated groupings, for example of the ethylene type or the acetylene type.

According to the present invention, therefore, new nitrogen-containing cellulose derivatives are produced by reacting upon a cellulose ester or ether containing-unsaturated groupings with nitrogen-containing organic compounds, and par-' ticularly organic bases containing a replaceable hydrogen atom attached to nitrogen. The treatment may take place, for example, at atmospheric temperature and pressure, or at increased temperatures and/or at increased pressure.

In the case of treating cellulose esters with the I organic bases the conditions are preferably so chosen that saponification of the ester by the base is either avoided altogether or is only partial. The tendency of bases to saponify the esters may be reduced or eliminated in a number of ways. For example I have found that the higher aliphatic bases have less tendency to saponify the ester than have the lower aliphatic bases or the strong cyclic bases. Further the amount of base 40 may be adjusted so that practically the whole of it combines with the unsaturated groupings in the cellulose ester, so that no excess remains for V effecting sapon'ification of the ester. In addition the reaction may be carried out under substantially anhydrous conditions, in which case dimethyl aniline or pyridi e may be present during the formation of the nitrogen-containing de- 7 for example acids of the aromatic series, as in the cellulose cinnamate, or of the alicyclic series. Again the'cellulose ethers may be simple unsaturated aliphatic ethers of cellulose, as for instance in allyl cellulose, vinyl cellulose or crotonyl cellulose, or of the cyclic series, as for instance in styryl cellulose (made from bromstyrene and alkali cellulose). All *the substituent groups on the cellulose molecule may be unsaturatedor part may be saturated and part unsaturated. Thus, for instance, in addition to the unsaturated ester,or ether groups the cellulose molecule may contain saturated ester or ether groups, as for instance acetyl, formyl, propionyl, butyryl, benzoyl, methyl, ethyl, propyl or benzyl groups, or oxyalkyl groups, as for example oxeyethyl groups. Two or more unsaturated ester or ether groups and/or two or more saturated ester or ether groups may be present. Mixed etheresters of cellulose may be employed, the whole or part of either the ether or the ester groups or both being unsaturated as for example in oxyethyl cellulose undecylenate and oxypropyl cellulose crotonate.

The initial ester or ether may if desired be in fibrous form, for example in a form in which it is obtained by esterification or etheriflcation of cotton or other cellulose yarn or fabric with the appropriate esterifying or etherifying agent with-. outresultant solution of the product, the process being similar to that employed in the production of immunized cotton.

The bases with which the cellulose derivatives are to be treated may also be of any desired series, for example of the aliphatic series, such as methylamine, ethylamine, propylamine, amylamine, hexylamine, and may, if desired, be substituted, as for example in monoor di-ethanolamine, propanolamine, 'dioxy-proplyamiue or the alcoholic amines obtainable by reduction of cyanides, for example ethylene oxide. Other sub- 'stituent groups, such as carboxy substituents, may be present 'in the base, as for instance in I genation'followed by amidation. In this connection it is to be noted that the use of amino acids affords another means of reducing saponification of a cellulose ester, since the presence ofthe .carboxy group or of other acid groups in the base to be used reduces the-basicity of the reagent. Esters of a no acids may also be employed, e. g.

methyl or et 1 glycine.

be used, for'example aniline, toluidinm, x'ylidines, cyclohexylamine, benzylamine, or their alkyl derivatives such as methyl, ethyl or benzyl aniline,

' or piperidine'. Urea, guani'dine and substituted ureas an'dguanidines are also useful especially. in the case of treating unsaturated cellulose.

ethers or in the case of making a halogenated cellulose derivative as an-intermediate product, as

described below. Other substances which con trogen may be used c. g. acetamide aiid benzamide.

creased'pressure, and similarly the use of ele- Tvated temperatures tends to increase the, nitrogen content of the resulting cellulose esters'or 0 ethers. The base may housed in the liquid state with the cellulose ester or ether in'the vapor state, e. g..by circulating the vapours of theorganic base through the unsaturated cellulose de-.

rivative. The reaction may be carried out with the base and thecellulose ester or etheralone or Y may be eilected in the presence of solvents" or diluents, for example ben zene, toluene, xylene,

. or other liquid hydrocarbons or alcohols. Preferably the solvent or diluent 'will not be itself capable of reaction with the organic base. In-

' stead of treating the unsaturated celluioseester or ether directly with the base, the ester or ether maynrst be halogenated as, for example, by direct treatment with mhloririe, bromine or other halogen, or by treatment with a halogenating compound, e. g. sulphuryl chloride or a halogen I acid, and the product then treated with the desired organic base to producethenitrogen-con- .60 taining cellulose derivative.

The following examples are-given in order to .illustrate the inventionbut'it is to be clearly undo not limit it in any way:- Example 1 I Bromine in carbon tetrachloride is introduced derstood that they gradually into a vessel containing allyl cellulose and carbon tetrachloride maintained at a temperature of 25-35 C. When no further absorption of bromine takes place the carbon tetra chloride and excess bromine are removed, pref-' erabiy under reducedpressure, and the cellulose derivative is carefullywashed with ligroin.

[A nitrogen-containing derivative is then chtained by heating the product with 2-3 times its the compounds obtainable by amldation of mayacids, whether unsaturated or not, or by halotimes weight of Iflpermme.

Substituted or unsubstituted cyclic bases may tain replaceable hydrogen atoms attached to ni- I carried out at ordinary atmospheric or reduced pressure, but is preferably effected "under in-' weight oi diethylamine at a temperature 0! '8O--1(l0 C. in'a closed vessel, if desired in the Y presence of a weak alkaline reagent such as calcium hydroxide. It is purified by distilling oflexcess diethylamine' andv washing with water or other non-solvent. 1 1

' 1 Example 2 Cellulose crotonate is heated either under reflux or in a closed. vessel at -120 C. with about 6-8 times its weightot benzene and 3-4 The nitrogencontaining derivative obtained is purified by heating under reduced pressure to remove the I A nitrogen-containing derivativemay be obtained by continuously circulatingthe vapours of aniline through cellulose cinnamate in the fi brous form. The reaction is carried out at slightly reduced pressure, e. g. at a pressure at which the aniline boils at Mir-160 C. On completion of the reaction the aniline present is removed by passing steam or nitrogen or, other inert gas throughthe vessel at a temperature of l00- C. In all the above-examples in which a liquid is employed it is desirable that the mixture be well .stirred'during the reaction.

The nitrogen-containing cellulose derivatives produced according to the present invention have i in common with those producedaccording to my ar where feasible it may be .broughtinto contact I. application 492,363 filed October 1930, an afilnity for acid wool colours, and for V most of the direct cotton colours. For this reason they "are valuable for the manufacture of textile materials, particularly when-used in conjunction with the known cellulose esters or ethers,

for example cellulose acetate, which lack amnity -for certain dyestufis. In addition to being sulta'ble for conversion into textile productsthe celused for the manufacture of plastic are pai-ticularly'useful where colouratl with sulphonated or like dyestufls is required, and for the manufacture of'flims, moulding powders and "the like. The plastic masses ormoulding powders maybe made up with ahysuitable plasticizing agents, as for instance those used in the manufacture of plastics from nitro-cellulose and cellulose acetate.

. In addition the cellulose derivativesoi the present invention may be used in the preparation of sizes for textile yarns and fabrics, and in this connection the cellulose derivatives which contain hydroxy groups or carboxy groups or other hydrophile' groups, whether present in the original cellulose ester or ether or present in the organic base with which such cellulose, ester is so treated, are particularly valuable. These'sizes inasmuch as theyhave an afilnity for'acid and direct colours may be the means of imparting fugitive tints with the aid of .acid wool or direct cotton colours to fibres, such as cellulose acetate, which havelittle or no afflnity for such colours.

Cellulose derivatives produced according to the present invention containing hydroxy or carboxy aoraero 3 substances may, it desired;'.be further treated to esteriiy or etheriiy such groups, ior example by treatment with acetic anhydrlde or other esterliying agent or by treatment with alcohol and sul- 6 phurlc acid. dlmethyl sulphate or other methylating or ethylatigng or like agents. 2r. 1 claim and desire to secure by Letters tent isz f 2 case for the manufacture of nitrogen- N containing cellulose derivatives which comprises reacting an organic base containing one or more replaceable hydrogen atoms a to nitrogen with a derivative oi cellulose containing an unsaturated grouping selected from the group consisting of cellulose ethers. carbowlic acid esters oi cellulose and ed cellulose ether-carboxylio acid 2. W for the nuiacture oi nitrogenwn cellulcse'derivatives which comprises 39 ting an o 1 containing one or-more replaceable hydrosen atoms attached tonitrogen with a cellulose rof an unsaturated ca'rbomlic acid.

atoms at s. lice. lilac oi nitrogencon close derivativw will comprises dvative or cellul from the w mile d escarbo'xyllc acid esters.

ters of cellulose, and mixed cellulose others-carboxyllc acid esters with a. halogenating agent and subsequently with an amine.

6. Process for the manufacture of nitrogen containing cellulose derivatives which comprises- 5 reacting an organic base containing one or more replaceable hydrogen atoms attached to nitrogen with a derivative oi cellulose containing an unsaturated grouping selected from the group consisting of cellulose ethers. carboxylic acid esters id of cellulose and mixed cellulose ether-carboxylic acid esters in an inert medium.

'3. Process for the manufacture of nitrogen containing cellulose derivatives which comprises reacting an organic base containing one or more 15 replaceable hydrogen atoms attached to nitrogen with a derivative of cellulose containing an unsaturated grouping selected from the group consisting of cellulose ethers, carboxylic acid esters of cellulose and mixed cellulose ether-carboxylic 2G acid esters and subjecting the products to esteriflcation or etheriflcation.

s. Nitrogen-containing cellulose derivatives obtained by reacting an organic base containing one or ore replaceable hydrogen atoms attached as to nitrogen with a derivativev of cellulose conan unsaturated grouping selected from the consisting of cellulose others, carbox'ylic acid esters of cellulose and mixed cellulose ether- 3G 9. Nitrogen-containing cellulose derivatives ob tained by. reacting an aliphatic amine containing at least four carbon atoms with a derivative of cellulose containing an unsaturated grouping selected irom the group consisting of cellulose as others, aylic acid esters of cellulose and ed cellulose ether-carboxylic acid esters. id. Nitrogen-containing cellulose derivatives obed by reacting an organic base containing v one or more replaceable hydrogen atoms attached as T to nitrogen with a cellulose ester oi an unsaturated who acid.

p Y DBEYFUS. 

